CN103896388A - Method for treating organic wastewater by using double catalysts to heterogeneously activate persulfates - Google Patents
Method for treating organic wastewater by using double catalysts to heterogeneously activate persulfates Download PDFInfo
- Publication number
- CN103896388A CN103896388A CN201410117176.5A CN201410117176A CN103896388A CN 103896388 A CN103896388 A CN 103896388A CN 201410117176 A CN201410117176 A CN 201410117176A CN 103896388 A CN103896388 A CN 103896388A
- Authority
- CN
- China
- Prior art keywords
- waste water
- organic waste
- dual catalyst
- persulphate
- heterogeneous
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Abstract
The invention discloses a method for treating organic wastewater by using double catalysts to heterogeneously activate persulfates, belonging to the technical field of water pollution control. According to the method, nano copper oxide and zero-valent iron particles are used as a combined catalyst to activate the persulfates to generate free sulfate radicals with strong oxidizing property, so that refractory organics are removed from the wastewater. Compared with a homogeneous persulfate water treatment technology, the method has the advantage that the heterogeneous catalysts can efficiently and continuously activate the persulfates to achieve a heterogeneous activation effect due to the properties of relatively large specific surface area, relatively high catalytic activity and the like. The double-catalyst heterogeneous persulfate activation water treatment technology established by the method disclosed by the invention is applicable to treatment of various kinds of organic wastewater, is high in efficiency, good in durability and convenient in operation, can efficiently remove toxic and harmful pollutants from the wastewater within a relatively wide pH range, provides a broad prospect for treating toxic, harmful and non-biodegradable organic wastewater, and has a great application potential in the field of environmental pollution treatment.
Description
Technical field
The invention belongs to technical field of water pollution control, be specifically related to a kind of method of utilizing the heterogeneous activation persulphate of dual catalyst to process organic waste water.
Background technology
Along with industry and agriculture fast development, the generation of Organic Pollutants in Wastewater and circulation problem serious threat ecotope and the mankind's health.Current Treatment of Industrial Water method mainly concentrates on physical treatment process, biological treatment and chemical method three major types.Physical treatment process is only realized alternate transfer, does not fundamentally realize thorough degraded and the mineralising of organic pollutant, is difficult to realize the advanced treatment of organic waste water; Although biological process has the features such as equipment operation is simple, and expense is low, for the pollutent of some poisonous difficult degradations, effect is also undesirable; And chemical method, the high-level oxidation technology being especially good at aspect advanced treatment, because its degradation efficiency is high, mineralization degree is large, easy to operate, is easy to control advantages such as non-secondary pollution and have very big development potentiality.
High-level oxidation technology can be divided into two large classes from the generation of free radical activity species: the oxidation system based on hydroxyl radical free radical (OH) and based on sulfate radical free radical (SO
4 -) oxidation system.Traditional high-level oxidation technology comprises that traditional Fenton process comprises the class Fenton process of development afterwards, its core is all based on produce OH deoxidation degradable organic pollutant with ferrous catalyzing hydrogen peroxide, but in Fenton system, still there are some problems: (1) is shorter to the requirement of pH higher (2) OH lifetime, in the aqueous solution, the life-span is less than 1us, cause its utilization ratio low (3) OH by addition and replace attack organic pollutant, can not effectively degrade to the organic pollutant of some special construction.
In high-level oxidation technology advanced treatment of waste water based on sulfate radical free radical, Persistent organic pollutants are a kind of advanced oxidation technology that development in recent years is got up.The SO that activation persulphate produces
4 -standard oxidationreduction potential be 2.6-3.1V, than OH, SO
4 -more stable under acid and neutrallty condition, SO under alkaline condition
4 -can be oxidized H
2o or OH
-generate OH, therefore in wider pH range, pollutent is all had to good degradation effect, these features have a extensive future the advanced oxidation technology based on sulfate radical free radical in the advanced treatment application of waste water.Decomposing persulphate by high temperature thermal activation, photochemical catalysis, microwave activation, gac activation, the mode such as transition metal-catalyzed can produce the sulfate radical free radical with strong oxidizing property and carry out the organic pollutant in oxidative degradation waste water.Wherein, thermal activation persulphate technology energy consumption is high, and photoactivation is relative with microwave activation persulphate technical qualification harsh, there is regeneration problem in gac activation, and transition metal activation is low for equipment requirements, and energy consumption is little, material benefit more economically, thereby have more application potential.But it is a lot of not enough that the ferrous persulfate oxidation reaction participating in exists, as the pH value of reaction requires to be acid, to actual waste water, application causes limitation for this; Excessive Fe in reaction system on the one hand
2+consume a large amount of SO
4 -, Fe on the other hand
2+can change into the Fe of on-catalytic activity
3+thereby, cause Fe
2+effective rate of utilization reduce; Fe in solution
2+very fast with persulphate speed of response, SO
4 -instantaneous a large amount of generation, oxidizing reaction moment completes, although speed of reaction is very high, SO
4 -effective rate of utilization reduce make the clearance of pollutent and mineralization rate all lower; In reaction process along with Fe
3+generation can produce a large amount of iron mud, the subsequent disposal of iron mud has not only increased processing cost, also can cause to environment pollution of solid waste etc.In the time of practical application, all there are the problems referred to above in traditional thermal activation, ferrous ion activation persulphate method.Cupric ion and iron ion catalysis persulphate have synergy, and adding of copper can make reaction more lasting, degrades more thorough.
Have not yet to see about nano cupric oxide and Zero-valent Iron Fe
0document and the patent report of dual catalyst activation persulfate oxidation.Domestic only have a method that has used monopersulfate salt, persulphate to produce sulfate radical free radical as Chinese patent CN101172691A discloses about the technology of homogeneous activation persulphate; CN102259993A discloses the method that uses the ferrous catalysis persulphate of different sorts complexing agent complexing degradation of organic waste water.The method of microwave cooperating gac using active persulphate for processing difficult-biodegradability organic waste water is disclosed about the patent report of heterogeneous activation persulphate as Chinese patent CN101525177A; Chinese patent CN102020350A discloses and has produced hydroxyl radical free radical oxidative degradation organic pollutants using the oxide compound of the oxide compound of iron and iron, cobalt and cobalt as catalyzer heterocatalysis Fenton reagent, has emphasized that transition-metals and their oxides can be used as the ability of catalyst activation Fenton reagent oxidize contaminants.In the present invention, embodied the mutual synergy of two kinds of metal catalysts, the interaction between two metal ion species makes reaction more lasting, is oxidized more thorough.But the technical matters of existing homogeneous phase, heterogeneous catalysis persulphate is more complicated, there is the condition restriction such as high pressure-temperature, UV-light, microwave, and the adsorption of gac makes catalyst deactivation and organic pollutant fail to remove completely, subsequent disposal problem not yet solves.
Summary of the invention
The object of the invention is to exist for existing persulphate active oxidation reaction system to require reaction system pH to be the too fast effective rate of utilization that makes persulphate of acid, oxidizing reaction low and produce the problems such as a large amount of iron mud, a kind of method of utilizing the heterogeneous activation persulphate of dual catalyst to process organic waste water is provided.
Object of the present invention is achieved through the following technical solutions:
A kind of method of utilizing the heterogeneous activation persulphate of dual catalyst to process organic waste water, using nano cupric oxide and Zero-valent Iron particulate composition material as dual catalyst, in organic waste water, add dual catalyst and oxygenant, under normal temperature condition, react, the organism in degradation of organic waste water.In described dual catalyst, the mass ratio of nano cupric oxide and Zero-valent Iron particulate is 1:1-1:5.
Specifically comprise the steps:
(1) the CODcr value of mensuration organic waste water;
(2) in organic waste water, add dual catalyst fully to mix;
(3) in the waste water of step (1), add oxygenant according to CODcr value, the waste water being fully purified after reaction.
In aforesaid method, described organic waste water comprises waste water from dyestuff or paper waste.
In aforesaid method, the concentration of described dual catalyst in organic waste water is 0.05-0.2g/L.
In aforesaid method, wherein said oxygenant is persulphate, comprises more than one in Sodium Persulfate, Potassium Persulphate or ammonium persulphate.
In aforesaid method, the concentration (mg/L) of wherein said oxygenant in organic waste water and the CODcr(mg/L of organic waste water) numeric ratio be controlled at 0.5:1-2:1.
In aforesaid method, the form of described nano cupric oxide is regular spheroidal particle, and particle diameter is 40-100nm; The form of Zero-valent Iron particulate is regular spheroidal particle, and particle diameter is 100-150um.
In aforesaid method, the pH value of described organic waste water is 3.0-9.0.
In aforesaid method, the reaction times of described reaction is 1-1.5 hour.
The present invention proposes the method for the heterogeneous activation persulphate processing of a kind of dual catalyst organic waste water.First there is the dissolving of iron and the decomposition of Sodium Persulfate on the surface of iron catalyst simultaneously, produced deliquescent iron ion (as Fe
2+and Fe
3+).With zero-valent iron particle Fe
0during for catalyzer, see formula 1, and no matter be under anaerobic or aerobic conditions, Fe
0the oxidizing reaction on surface all can produce the Fe with catalysis persulphate ability
2+, see formula 2,3.Fe
0surperficial Fe
2+and the electric transmission between persulfate produces the sulfate radical free radical of strong oxidizing property by organic pollutant oxidative degradation, this is Heterogeneous oxidation reaction.Fe in the aqueous solution simultaneously
2+also can react with persulphate generation homogeneous oxidizing, see formula 4.Produce subsequently the Fe without catalytic capability
3+but, Fe
3+at Fe
0surface can be by transfer transport to Fe
2+transform, see formula 5, this reaction can improve the homogeneous catalysis degradation capability of this system.In addition, along with the carrying out of reaction, Fe
0the oxide compound of Surface Creation simultaneously also can by with Fe
0between the transfer activation persulphate degraded of electronics be adsorbed on Fe
0the pollutent on surface, is shown in formula 6.During taking nano cupric oxide as catalyzer, see formula 7, meanwhile, the Cu in the aqueous solution
2+react with persulphate, see formula 8.In reaction process, Cu
2+with Fe
0react, see formula 9, the cupric ion in the aqueous solution is present in Zero-valent Iron surface, has accelerated to a certain extent Fe
0to Fe
2+conversion, make the surface of Zero-valent Iron have Cu
2+with Fe
2+compound ion, accelerate decomposition persulphate produces sulfate radical free radical.And on the one hand because nano cupric oxide own is very slow with reacting of persulphate, can not consume in a large number sulfate radical free radical; Cu on the other hand
2+catalysis be a kind of catalytic capability of lasting type, can make the degraded of organic pollutant more thorough, mineralization rate is higher.
The sulfate radical free radical that dual catalyst activation persulfate oxidation system produces, mainly by capturing hydrogen from saturated carbon atom and providing the mode of electronics to react with organic pollutant to unsaturated carbon, is shown in formula 10.SO
4 -more stable in neutral and acidic aqueous solution, but in the time of pH>9, SO
4 -oxidizing water or OH
-generate OH, see formula 11,12, the OH producing in system is mainly by capturing the hydrogen on c h bond in organism, N-H key or O-H key, see formula 13, react with the two keys of C==C or aromatic ring, see formula 14, the intermediate product of organic pollutant further reaction under the effect of these free radicals subsequently, is finally degraded to CO
2, H
2o and nontoxic small-molecule substance.Therefore the SO that, utilizes persulphate itself and activation thereof to produce
4 -, OH living radical carries out the degraded of organic pollutant, will have potential using value in environmental pollution improvement field.
Fe
0+S
2O
8 2-→Fe
2++2SO
4 2- (1)
Fe
0+2H
2O→Fe
2++2OH
-+H
2 (2)
2Fe
0+O
2+2H
2O→2Fe
2++4OH
- (3)
Fe
2++S
2O
8 2-→Fe
3++SO
4 -·+SO
4 2- (4)
Fe
0+2Fe
3+→3Fe
2+ (5)
Fe
2+ iron oxide+S
2O
8 2-→Fe
3+ iron oxide+SO
4 -·+SO
4 2- (6)
CuO+S
2O
8 2-+2H
+→Cu
3++SO
4 -·+SO
4 2-+H
2O (7)
Cu
2++S
2O
8 2-→Cu
3++SO
4 -·+SO
4 2- (8)
Cu
2++Fe
0→Cu+Fe
2+(9)
SO
4 -·+RH→R·+SO
4 2-+H
+ (10)
SO4
-·+H2O→HSO4
-+·OH (11)
SO
4 -·+OH
-→SO
4 2-+·OH(12)
RH+·OH→R·+H
2O (13)
RH+·OH→RHOH· (14)
Compared with prior art, advantage of the present invention:
(1) provided by the invention with dual catalyst activation persulfate oxidation treatment technology, because using nano cupric oxide, Zero-valent Iron Fe
0material forms homogeneous phase and heterogeneous two kinds of catalyzed oxidation actings in conjunction as dual catalyst, the high catalytic activity of two metal ion species and transfer transport each other, redox can effectively be decomposed persulphate to produce sulfate radical free radical, and the utilization ratio of free radical is high, the reaction times is short, good to the removal effect of pollutent.
(2) the inventive method is at normal temperature, without getting final product efficient degradation Organic Pollutants in Wastewater under illumination condition, and the synergy of dual catalyst is widened its waste water ph that is applicable to process greatly, and the persulphate of catalysis lastingly makes it constantly produce living radical.
(3) the dual catalyst consumption in the inventive method is less, wide material sources, and post catalyst reaction is easier to recycle and reuse from solution.
(4) negatively charged ion (Cl of dual catalyst activation persulfate oxidation treatment technology provided by the invention because using nano cupric oxide, Zero-valent Iron microparticle material to make system avoid molysite to introduce
-, SO
4 2-deng) the new pollution that causes, and the Fe separating out in system
2+concentration is not high, both can effective activation persulphate, avoid again a large amount of generations and the subsequent disposal of iron mud.
(5) the present invention is simple to operate, and persistence is good, and efficiency is high, and economically feasible is suitable for the advanced treatment of various organic waste waters.
Brief description of the drawings
Fig. 1 is the process flow sheet that utilizes the heterogeneous efficient activation persulphate of dual catalyst to process organic waste water of the present invention.
Fig. 2 is that the present invention processes the design sketch of (being called for short OG) of orange G in water, wherein, a is the effect curve that only adds persulphate degraded OG, b is the effect curve that adds separately Zero-valent Iron particulate degraded OG, c is the effect curve that adds separately nano oxidized copper degradation OG, d is the effect curve that adds single catalyzer Zero-valent Iron particulate and persulphate degraded OG, e is the effect curve that adds single catalyst nano cupric oxide and persulphate degraded OG, and f is the effect curve that adds dual catalyst and persulphate degraded OG.
Fig. 3 is the technical schematic diagram that utilizes the heterogeneous efficient activation persulphate of dual catalyst to process organic waste water of the present invention.
Embodiment
Below by embodiment, the invention will be further described, illustrates outstanding feature of the present invention and marked improvement, is only the present invention is described and is in no way limited to following instance.
The embodiment of the present invention is selected the representative of azoic dyestuff orange G as waste water from dyestuff pollutent, selects the representative of the actual paper waste of Zhong Shanmou factory as paper waste.
The present embodiment compared utilize separately persulphate, separately catalyzer, utilize Zero-valent Iron activation persulphate separately, utilize nano cupric oxide activation persulphate separately, utilize waste water from dyestuff under four kinds of modes of dual catalyst activation persulphate with chroma removal rate and CODcr clearance.
Concrete operation step is as follows:
(1) according to the flow sequence shown in Fig. 1, get waste water from dyestuff, the CODcr that surveys waste water is 300mg/L, and pH is 6.8.Adopting 250mL Erlenmeyer flask is reactor, adds 200mL waste water.
(2) in above-mentioned Erlenmeyer flask reactor, add dual catalyst, the preparation method of dual catalyst is as follows: nano cupric oxide particle is evenly mixed according to the quality proportioning of 1:2 with Zero-valent Iron particulate.
(3) adding nano cupric oxide dosage in catalyzer is 0.05g/L, and the dosage of Zero-valent Iron particulate is 0.1g/L.
(4) in the reactor of step (1), respectively add Sodium Persulfate 238mg/L again, under normal temperature, react, the reaction times is 1h.
In addition, in order to compare, increase following two comparative examples:
1, add separately in catalyst experiment, do not need to add Sodium Persulfate, other conditions are the same.
2, add separately in Sodium Persulfate experiment, do not need to add catalyzer, other conditions are the same.
As shown in Figure 2 and Table 1, Fig. 2 X-coordinate is the reaction times to result, and ordinate zou represents the residual concentration of OG and the ratio of starting point concentration.
Fig. 2 and table 1 result show, single catalyzer and separately Sodium Persulfate technique all fail dyeing waste water effectively to decolour, and chroma removal rate and the CODcr clearance of single catalyst activation Sodium Persulfate technique are not high.And the obvious processing effect of dual catalyst activation Sodium Persulfate.The present invention is treatment of dyeing and printing fast and effeciently, and after reaction 60min, percent of decolourization reaches 96%, COD
crclearance is also higher.
The comparison of table 1 different process
| Processing condition | Percent of decolourization | CODcr clearance |
| Sodium Persulfate separately | 1.15% | 0.56% |
| Zero-valent Iron particulate separately | 1.36% | 0.78% |
| Nano cupric oxide separately | 1.29% | 0.74% |
| Zero-valent Iron activation Sodium Persulfate | 60.7% | 32.9% |
| Nano cupric oxide Sodium Persulfate | 12.3% | 4.63% |
| Dual catalyst activation Sodium Persulfate | 96.9% | 60.35% |
As shown in Figure 3, principle of the present invention is Zero-valent Iron and nano cupric oxide catalysis persulphate generation sulfate radical free radical altogether.In catalyst activation procedure, the cupric ion homogeneous activation persulphate in ferrous ion and the cupric oxide of Zero-valent Iron stripping produces living radical degraded target contaminant; Meanwhile, also there is heterogeneous catalysis effect in Zero-valent Iron and nano cupric oxide surface; Also there is the carrying out of redoxomorphism accelerated reaction in the cupric ion in system and Zero-valent Iron, make oxygenizement more lastingly, thoroughly complete.
Embodiment 2
Utilize the heterogeneous efficient activation persulphate of dual catalyst to process a method for organic waste water, concrete operation step is as follows:
(1) get waste water from dyestuff, the CODcr that surveys waste water is 300mg/L, and pH is 6.8.Adopting 250mL Erlenmeyer flask is reactor, adds 200mL waste water.Regulating respectively pH value is 3,5,7,9.
(2) in above-mentioned Erlenmeyer flask reactor, add catalyzer, in catalyzer, nano cupric oxide dosage is that the dosage of 0.05g/L Zero-valent Iron particulate is 0.1g/L.
(3) in the reactor of step (2), respectively add Sodium Persulfate 238mg/L again, under normal temperature, react, the reaction times is 1h.
Its result is as shown in table 2, the result of table 2 shows, the method of the heterogeneous degradation of organic waste water of dual catalyst activation persulphate that the present invention sets up all can have good decolorizing effect to dyeing waste water under acid, neutrality, alkaline condition, save and thrown sour expense, ensured the high efficiency of persulphate technology.And the percent of decolourization of waste water all reaches more than 90%, COD
crclearance reaches more than 48.4%, treatment effect the best under acidic conditions, and the consumption of dual catalyst is few, is easy to reclaim, pollution-free.
The dual catalyst activation Sodium Persulfate degraded dyeing waste water of the different initial pH value of table 2
Embodiment 3
Utilize the heterogeneous efficient activation persulphate of dual catalyst to process a method for organic waste water, concrete operation step is as follows:
(1) get waste water from dyestuff, the CODcr that surveys waste water is 300mg/L, and pH is 6.8.Adopting 250mL Erlenmeyer flask is reactor, adds 200mL waste water.
(2) in above-mentioned Erlenmeyer flask reactor, add catalyzer, in catalyzer, nano cupric oxide dosage is that the dosage of 0.05g/L Zero-valent Iron particulate is 0.1g/L.
(3) in the reactor of step (2), respectively add Sodium Persulfate 238mg/L again, under normal temperature, react, the reaction times is 1h.
Its result is as shown in table 3, and the result of table 3 shows that the method for the heterogeneous degradation of organic waste water of dual catalyst activation persulphate that the present invention sets up has ensured persistence and the high efficiency of persulphate method.
Two kinds of persulphate method degradation of dye waste water of table 3
Embodiment 4
Embodiment has investigated the recycling effect of catalyzer in the heterogeneous activation persulphate processing of dual catalyst organic waste water method, and concrete operation step is as follows:
(1) get waste water from dyestuff, the CODcr that surveys waste water is 300mg/L, and pH is 6.8.Adopting 250mL Erlenmeyer flask is reactor, adds 200mL waste water.
(2) catalyzer after front primary first-order equation is filtered, for subsequent use after vacuum-drying 12h.
(3) in above-mentioned Erlenmeyer flask reactor, add catalyzer in step (2).
(4) in the reactor of step (3), respectively add Sodium Persulfate 238mg/L again, under normal temperature, react, the reaction times is 1h.
Result is as shown in table 4, table 4 result shows, along with catalyzer is reused the increase of number of times, dual catalyst activation Sodium Persulfate technique declines to some extent to the processing power of waste water, but recycle effect with respect to prior art, its effect is superior, and catalyzer is easier to recycle and reuse from solution.
Table 4 catalyst recovery is reused effect
| Reuse number of times | Percent of | CODcr clearance | |
| 0 time | 96.9% | 60.35% | |
| 1 time | 87.7% | 57.47% | |
| 2 times | 74.8% | 52.12% | |
| 3 times | 64.1% | 43.76% |
Utilize the heterogeneous efficient activation persulphate of dual catalyst to process a method for organic waste water, concrete operation step is as follows:
Concrete operation step is as follows:
(1) the actual papermaking secondary biochemical effluent of Qu Zhongshanmou factory, the CODcr that surveys waste water is 120mg/L, pH is 7.1.Adopting 250mL Erlenmeyer flask is reactor, adds 200mL waste water.
(2) in above-mentioned Erlenmeyer flask reactor, add catalyzer, in catalyzer, nano cupric oxide dosage is that the dosage of 0.05g/L Zero-valent Iron particulate is 0.1g/L.
(3) in the reactor of step (2), respectively add Sodium Persulfate 238mg/L again, under normal temperature, react, the reaction times is 1h.
Its result is as shown in table 5, and the method that the result of table 5 shows the heterogeneous degradation of organic waste water of dual catalyst activation persulphate that the present invention sets up has also kept good degradation effect processing in organic waste water not of the same race.
The treatment effect of table 5 paper mill secondary biochemical effluent
| Processing condition | Percent of decolourization | CODcr clearance |
| Sodium Persulfate separately | 0.50% | 0.21% |
| Zero-valent Iron activation Sodium Persulfate | 47.4% | 27.6% |
| Nano cupric oxide Sodium Persulfate | 9.8% | 2.74% |
| Dual catalyst activation Sodium Persulfate | 85.3% | 54.7% |
Above-described embodiment is preferably embodiment of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and principle, substitutes, combination, simplify; all should be equivalent substitute mode, within being included in protection scope of the present invention.
Claims (10)
1. a method of utilizing the heterogeneous activation persulphate of dual catalyst to process organic waste water, it is characterized in that, using nano cupric oxide and Zero-valent Iron particulate composition material as dual catalyst, in organic waste water, add dual catalyst and oxygenant, under normal temperature condition, react the organism in degradation of organic waste water.
2. utilize according to claim 1 the heterogeneous activation persulphate of dual catalyst to process the method for organic waste water, it is characterized in that: in described dual catalyst, the mass ratio of nano cupric oxide and Zero-valent Iron particulate is 1:1-1:5.
3. according to utilizing the heterogeneous activation persulphate of dual catalyst to process the method for organic waste water described in claims 1, it is characterized in that: the concrete steps of described method are:
(1) the CODcr value of mensuration organic waste water;
(2) in organic waste water, add dual catalyst fully to mix;
(3) in the waste water of step (1), add oxygenant according to CODcr value, the waste water being fully purified after reaction.
4. according to utilizing the heterogeneous activation persulphate of dual catalyst to process the method for organic waste water described in claims 3, it is characterized in that: described organic waste water comprises waste water from dyestuff or paper waste.
5. according to utilizing the heterogeneous activation persulphate of dual catalyst to process the method for organic waste water described in claims 3, it is characterized in that: the concentration of described dual catalyst in organic waste water is 0.05-0.2g/L.
6. according to utilizing the heterogeneous activation persulphate of dual catalyst to process the method for organic waste water described in claims 3, it is characterized in that: described oxygenant is persulphate, comprise more than one in Sodium Persulfate, Potassium Persulphate or ammonium persulphate.
7. according to utilizing the heterogeneous activation persulphate of dual catalyst to process the method for organic waste water described in claims 3, it is characterized in that: the concentration (mg/L) of described oxygenant in organic waste water and the CODcr(mg/L of organic waste water) numeric ratio be controlled at 0.5:1-2:1.
8. utilize according to claim 3 the heterogeneous activation persulphate of dual catalyst to process the method for organic waste water, it is characterized in that: the form of described nano cupric oxide is regular spheroidal particle, particle diameter is 40-100nm; The form of Zero-valent Iron particulate is regular spheroidal particle, and particle diameter is 100-150um.
9. utilize according to claim 3 the heterogeneous activation persulphate of dual catalyst to process the method for organic waste water, it is characterized in that: the pH value of described organic waste water is 3.0-9.0.
10. utilize according to claim 3 the heterogeneous activation persulphate of dual catalyst to process the method for organic waste water, it is characterized in that: the reaction times of described reaction is 1-1.5 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410117176.5A CN103896388B (en) | 2014-03-26 | 2014-03-26 | A kind of method utilizing the heterogeneous organic wastewater treatment through persulfate activation of dual catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410117176.5A CN103896388B (en) | 2014-03-26 | 2014-03-26 | A kind of method utilizing the heterogeneous organic wastewater treatment through persulfate activation of dual catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103896388A true CN103896388A (en) | 2014-07-02 |
| CN103896388B CN103896388B (en) | 2016-07-06 |
Family
ID=50988020
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410117176.5A Active CN103896388B (en) | 2014-03-26 | 2014-03-26 | A kind of method utilizing the heterogeneous organic wastewater treatment through persulfate activation of dual catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103896388B (en) |
Cited By (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104176812A (en) * | 2014-08-16 | 2014-12-03 | 复旦大学 | Sewage treatment method and device by taking zero-valent iron powder as carrier |
| CN104310565A (en) * | 2014-10-15 | 2015-01-28 | 济南大学 | Method of treating organic wastewater based on Fenton-like reaction of iron-based organic-framework material |
| CN104710061A (en) * | 2015-02-12 | 2015-06-17 | 重庆安欣环保节能科技有限公司 | Drilling wastewater treatment method capable of catalyzing sulfate radicals based on ultraviolet composite catalyst |
| CN104909427A (en) * | 2015-05-11 | 2015-09-16 | 北京林业大学 | Construction and application method of photoassisted porous copper bismuthate activated persulfate water treatment high-grade oxidation technology |
| CN104944565A (en) * | 2015-05-07 | 2015-09-30 | 北京科技大学 | Novel multi-free-radical synergistic effect water treatment method under plasma environment |
| CN105110448A (en) * | 2015-10-09 | 2015-12-02 | 中国科学院南海海洋研究所 | Method for removing heavy metal and organic matter composite pollutants in water body by means of zero-valent iron and persulfate |
| CN105214738A (en) * | 2015-10-28 | 2016-01-06 | 北京师范大学 | Catalyst based and the wet dip preparation method of a kind of efficient carbon nanofiber |
| CN105253983A (en) * | 2015-09-30 | 2016-01-20 | 中山大学 | Water treatment method of zero-valent iron-copper bi-metal activated persulfate |
| CN106007054A (en) * | 2016-05-25 | 2016-10-12 | 广东工业大学 | Method for treating aluminum diethyl phosphinate wastewater. |
| CN106495377A (en) * | 2016-11-16 | 2017-03-15 | 安徽工程大学 | A kind of processing method of complexation nickel waste water |
| CN106587325A (en) * | 2016-12-19 | 2017-04-26 | 华南理工大学 | Method for treating difficult-to-degrade wastewater by non-homogeneously activating peroxymonosulfate through CoxFe1-xP material |
| CN106943871A (en) * | 2017-03-09 | 2017-07-14 | 华北电力大学 | A kind of method that low temperature class catalytic gas phase oxidation removes flue gas multiple pollutant |
| CN106955708A (en) * | 2017-04-24 | 2017-07-18 | 西安科技大学 | A kind of method for activating persulfate Fourier Series expansion technique degraded Organic substance in water |
| CN107416961A (en) * | 2017-04-17 | 2017-12-01 | 同济大学 | By Fe2+Agent and the agent of compound RAPD check and its application of CuO compositions |
| CN107720925A (en) * | 2017-09-14 | 2018-02-23 | 安徽工程大学 | Utilize the method for sodium sulfite activation persulfate degraded methyl orange azo dye wastewater |
| CN108046405A (en) * | 2018-01-23 | 2018-05-18 | 新疆大学 | The CuO/ persulfate oxidation agent of oxidative degradation dyestuff |
| CN108059229A (en) * | 2017-12-20 | 2018-05-22 | 苏州科技大学 | A kind of method of iron carbon activation persulfate processing high-concentration hardly-degradable alkaline waste liquor |
| CN109292951A (en) * | 2018-09-19 | 2019-02-01 | 合肥学院 | It is a kind of to utilize MnOX/Fe0The method of nanocomposite organic wastewater treatment through persulfate activation |
| CN109305723A (en) * | 2018-12-10 | 2019-02-05 | 华侨大学 | A kind of minimizing technology of organic pollutants |
| CN110697864A (en) * | 2019-05-22 | 2020-01-17 | 北京万邦达环保技术股份有限公司 | Ultrasonic coupling integrated wastewater treatment device, method and system |
| CN110697865A (en) * | 2019-05-22 | 2020-01-17 | 北京万邦达环保技术股份有限公司 | Ultrasonic coupling integrated wastewater treatment device, method and system |
| CN111450829A (en) * | 2020-05-06 | 2020-07-28 | 青岛理工大学 | Copper oxide nano catalytic film for catalyzing persulfate to degrade organic wastewater and preparation method thereof |
| CN111892153A (en) * | 2020-06-17 | 2020-11-06 | 中国科学技术大学 | Low-energy-consumption high-efficiency direct oxidation transfer water treatment process |
| CN112062258A (en) * | 2020-09-16 | 2020-12-11 | 天津理工大学 | Method for degrading aniline by using copper oxide persulfate system without free radical mechanism |
| CN112978984A (en) * | 2021-02-07 | 2021-06-18 | 宁波财经学院 | Organic wastewater treatment device |
| CN114768509A (en) * | 2022-04-01 | 2022-07-22 | 中北大学 | Method and device for removing multi-component pollutants in flue gas based on supergravity technology |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102583692A (en) * | 2011-12-16 | 2012-07-18 | 华南理工大学 | Method for treating organic pollutants in water by catalyzing persulfate through heterogeneous copper oxide |
| CN103058346A (en) * | 2011-10-18 | 2013-04-24 | 中国石油化工股份有限公司 | Wastewater treatment method |
| WO2013100262A1 (en) * | 2011-12-29 | 2013-07-04 | Woongjincoway Co., Ltd. | Method for treating water containing organics |
| CN103435144A (en) * | 2013-08-27 | 2013-12-11 | 华南理工大学 | Method for utilizing heterogeneous catalyst to efficiently activate persulfate so as to treat organic wastewater |
-
2014
- 2014-03-26 CN CN201410117176.5A patent/CN103896388B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103058346A (en) * | 2011-10-18 | 2013-04-24 | 中国石油化工股份有限公司 | Wastewater treatment method |
| CN102583692A (en) * | 2011-12-16 | 2012-07-18 | 华南理工大学 | Method for treating organic pollutants in water by catalyzing persulfate through heterogeneous copper oxide |
| WO2013100262A1 (en) * | 2011-12-29 | 2013-07-04 | Woongjincoway Co., Ltd. | Method for treating water containing organics |
| CN103435144A (en) * | 2013-08-27 | 2013-12-11 | 华南理工大学 | Method for utilizing heterogeneous catalyst to efficiently activate persulfate so as to treat organic wastewater |
Cited By (35)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104176812A (en) * | 2014-08-16 | 2014-12-03 | 复旦大学 | Sewage treatment method and device by taking zero-valent iron powder as carrier |
| CN104310565A (en) * | 2014-10-15 | 2015-01-28 | 济南大学 | Method of treating organic wastewater based on Fenton-like reaction of iron-based organic-framework material |
| CN104310565B (en) * | 2014-10-15 | 2016-03-02 | 济南大学 | A kind of based on iron-based organic-method of the embryonic stem-like cells process organic waste water of framework material |
| CN104710061A (en) * | 2015-02-12 | 2015-06-17 | 重庆安欣环保节能科技有限公司 | Drilling wastewater treatment method capable of catalyzing sulfate radicals based on ultraviolet composite catalyst |
| CN104944565A (en) * | 2015-05-07 | 2015-09-30 | 北京科技大学 | Novel multi-free-radical synergistic effect water treatment method under plasma environment |
| CN104909427A (en) * | 2015-05-11 | 2015-09-16 | 北京林业大学 | Construction and application method of photoassisted porous copper bismuthate activated persulfate water treatment high-grade oxidation technology |
| CN104909427B (en) * | 2015-05-11 | 2018-04-20 | 北京林业大学 | A kind of light helps the member persulfate method for treating water of porous bismuthic acid |
| CN105253983A (en) * | 2015-09-30 | 2016-01-20 | 中山大学 | Water treatment method of zero-valent iron-copper bi-metal activated persulfate |
| CN105110448B (en) * | 2015-10-09 | 2017-11-07 | 中国科学院南海海洋研究所 | A kind of method that utilization Zero-valent Iron persulfate removes the organic compound contaminated water body of removing heavy metals simultaneously |
| CN105110448A (en) * | 2015-10-09 | 2015-12-02 | 中国科学院南海海洋研究所 | Method for removing heavy metal and organic matter composite pollutants in water body by means of zero-valent iron and persulfate |
| CN105214738A (en) * | 2015-10-28 | 2016-01-06 | 北京师范大学 | Catalyst based and the wet dip preparation method of a kind of efficient carbon nanofiber |
| CN106007054A (en) * | 2016-05-25 | 2016-10-12 | 广东工业大学 | Method for treating aluminum diethyl phosphinate wastewater. |
| CN106495377A (en) * | 2016-11-16 | 2017-03-15 | 安徽工程大学 | A kind of processing method of complexation nickel waste water |
| CN106495377B (en) * | 2016-11-16 | 2019-05-10 | 安徽工程大学 | A kind of processing method that nickel waste water is complexed |
| CN106587325A (en) * | 2016-12-19 | 2017-04-26 | 华南理工大学 | Method for treating difficult-to-degrade wastewater by non-homogeneously activating peroxymonosulfate through CoxFe1-xP material |
| CN106587325B (en) * | 2016-12-19 | 2020-05-22 | 华南理工大学 | By using CoxFe1-xMethod for treating refractory wastewater by using P material heterogeneous activated monopersulfate |
| CN106943871A (en) * | 2017-03-09 | 2017-07-14 | 华北电力大学 | A kind of method that low temperature class catalytic gas phase oxidation removes flue gas multiple pollutant |
| CN106943871B (en) * | 2017-03-09 | 2023-07-14 | 华北电力大学 | Method for removing multi-pollutants in flue gas by low-temperature gas-phase catalytic oxidation |
| CN107416961A (en) * | 2017-04-17 | 2017-12-01 | 同济大学 | By Fe2+Agent and the agent of compound RAPD check and its application of CuO compositions |
| CN106955708A (en) * | 2017-04-24 | 2017-07-18 | 西安科技大学 | A kind of method for activating persulfate Fourier Series expansion technique degraded Organic substance in water |
| CN107720925A (en) * | 2017-09-14 | 2018-02-23 | 安徽工程大学 | Utilize the method for sodium sulfite activation persulfate degraded methyl orange azo dye wastewater |
| CN108059229A (en) * | 2017-12-20 | 2018-05-22 | 苏州科技大学 | A kind of method of iron carbon activation persulfate processing high-concentration hardly-degradable alkaline waste liquor |
| CN108046405A (en) * | 2018-01-23 | 2018-05-18 | 新疆大学 | The CuO/ persulfate oxidation agent of oxidative degradation dyestuff |
| CN109292951A (en) * | 2018-09-19 | 2019-02-01 | 合肥学院 | It is a kind of to utilize MnOX/Fe0The method of nanocomposite organic wastewater treatment through persulfate activation |
| CN109292951B (en) * | 2018-09-19 | 2021-04-02 | 合肥学院 | By using MnOX/Fe0Method for treating organic wastewater by activating persulfate through nano composite material |
| CN109305723A (en) * | 2018-12-10 | 2019-02-05 | 华侨大学 | A kind of minimizing technology of organic pollutants |
| CN110697864A (en) * | 2019-05-22 | 2020-01-17 | 北京万邦达环保技术股份有限公司 | Ultrasonic coupling integrated wastewater treatment device, method and system |
| CN110697865A (en) * | 2019-05-22 | 2020-01-17 | 北京万邦达环保技术股份有限公司 | Ultrasonic coupling integrated wastewater treatment device, method and system |
| CN111450829B (en) * | 2020-05-06 | 2022-05-31 | 青岛理工大学 | Copper oxide nano catalytic film for catalyzing persulfate to degrade organic wastewater and preparation method thereof |
| CN111450829A (en) * | 2020-05-06 | 2020-07-28 | 青岛理工大学 | Copper oxide nano catalytic film for catalyzing persulfate to degrade organic wastewater and preparation method thereof |
| CN111892153A (en) * | 2020-06-17 | 2020-11-06 | 中国科学技术大学 | Low-energy-consumption high-efficiency direct oxidation transfer water treatment process |
| CN112062258A (en) * | 2020-09-16 | 2020-12-11 | 天津理工大学 | Method for degrading aniline by using copper oxide persulfate system without free radical mechanism |
| CN112978984A (en) * | 2021-02-07 | 2021-06-18 | 宁波财经学院 | Organic wastewater treatment device |
| CN114768509A (en) * | 2022-04-01 | 2022-07-22 | 中北大学 | Method and device for removing multi-component pollutants in flue gas based on supergravity technology |
| CN114768509B (en) * | 2022-04-01 | 2023-12-01 | 中北大学 | Method and device for removing multi-component pollutants in flue gas based on supergravity technology |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103896388B (en) | 2016-07-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103896388A (en) | Method for treating organic wastewater by using double catalysts to heterogeneously activate persulfates | |
| CN103435144B (en) | A kind of method utilizing the efficient organic wastewater treatment through persulfate activation of heterogeneous catalyst | |
| Bello et al. | A review on approaches for addressing the limitations of Fenton oxidation for recalcitrant wastewater treatment | |
| Chen et al. | Landfill leachate treatment by persulphate related advanced oxidation technologies | |
| Manna et al. | Advanced oxidation process: a sustainable technology for treating refractory organic compounds present in industrial wastewater | |
| CN106554126B (en) | Deep standard-reaching treatment method and system for reverse osmosis concentrated water | |
| CN102020350A (en) | Processing method of heterocatalysis persulfate Fenton oxidation water | |
| CN102173500A (en) | Method for treating water by Fenton oxidization of activated molecular oxygen | |
| WO2018184391A1 (en) | Method for synchronously removing complex heavy metal and organic substance by magnetic separation | |
| Chen et al. | Regeneration performance of spent granular activated carbon for tertiary treatment of dyeing wastewater by Fenton reagent and hydrogen peroxide | |
| CN110357347B (en) | Method for treating wastewater by persulfate advanced oxidation coupling biological sulfate reduction | |
| CN102167435B (en) | Solid catalytic Fenton water treatment technique | |
| CN103708647A (en) | Deep treatment method for industrial wastewater through natural pyrite catalyzed H2O2 oxidation | |
| CN114054059A (en) | Method for degrading sulfamethoxazole in wastewater by activating persulfate through magnetic two-dimensional Mxene/CuFeO2 catalyst | |
| CN113929197B (en) | Method for treating organic wastewater by activating peroxymonosulfate with assistance of visible light | |
| CN106732610A (en) | A kind of preparation method and application of Ni doped magnetics charcoal class fenton catalyst | |
| CN102583679A (en) | Method for treating petrochemical waste water and biochemical tail water through recycled coagulant | |
| CN110606539B (en) | Method for treating organic wastewater by utilizing sludge resource | |
| CN111606519A (en) | Advanced treatment method for electroplating wastewater | |
| CN107324587B (en) | Method for synchronously removing heavy metals and organic matters in wastewater | |
| CN105254091A (en) | Method for treating organic wastewater difficult to biochemically degrade | |
| CN111392845A (en) | Composition for degrading organic pollutants as well as preparation method and application thereof | |
| CN108147591B (en) | Method for treating high-concentration alkaline resin desorption solution by catalytic ozone oxidation technology | |
| CN106587325B (en) | By using CoxFe1-xMethod for treating refractory wastewater by using P material heterogeneous activated monopersulfate | |
| CN114105277B (en) | Method for removing organic pollutants in water by catalyzing hydrogen peroxide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |